Integrated electrokinetic processes for the remediation of phthalate esters in river sediments: A mini-review.

Concerning the contamination of phthalate esters (PAEs) in river sediments, this mini-review introduces four recently reported novel "integrated electrokinetic (EK) processes" for the remediation purpose, namely two combined technologies of the EK process and advanced oxidation process (EK-AOP Processes) and two combined technologies of the EK process and biological process (EK-BIO Processes). The following is a comprehensive summary for these remediation processes: (1) the EK process coupled with nano-Fe3O4/S2O82- oxidation process - Test results have shown that nanoscale Fe3O4 played a significant role in activating persulfate oxidation. Even a recalcitrant compound like di(2­ethylhexyl)phthalate (DEHP), its concentration in test sediment was reduced to 1.97 mg kg-1, far below the regulatory levels set by Taiwan EPA; (2) the EK process integrated with a novel Fenton-like process catalyzed by nanoscale schwertmannite (nano-SHM) - Test results have revealed that simultaneous injection of nano-SHM slurry and H2O2 into the anode reservoir and sediment compartment is a good practice. 70-99% in removal efficiency was obtained for various target PAEs; (3) enhanced in situ bioremediation coupled with the EK process for promoting the growth of intrinsic microorganisms by adding H2O2 as an oxygen release compound (ORC) - Test results have demonstrated that an intermittent mode of injecting lab-prepared ORC directly into the contaminant zone would be beneficial to the growth of intrinsic microorganisms in test sediment for in situ bioremediation of target PAEs; and (4) coupling of a second-generation ORC (designated 2G-ORC) with the EK-biological process - Test results have proved that 2G-ORC is long-lasting and can be directly utilized as the carbon source and oxygen source for microbial growth resulting in an enhanced biodegradation of PAEs. Except DEHP having a residual concentration of 4 µg kg-1, all other target PAEs in test sediment were totally removed by this novel combined remediation process.

Removal of micropollutants from municipal wastewater by graphene adsorption and simultaneous electrocoagulation/electrofiltration process.

In this work the optimal operating conditions for removing selected micropollutants (also known as emerging contaminants, ECs) from actual municipal wastewater by graphene adsorption (GA) and simultaneous electrocoagulation/electrofiltration (EC/EF) process, respectively, were first determined and evaluated. Then, performance and mechanisms for the removal of selected phthalates and pharmaceuticals from municipal wastewater simultaneously by the GA and EC/EF process were further assessed. ECs of concern included di-n-butyl phthalate (DnBP), di-(2-ethylhexyl) phthalate (DEHP), acetaminophen (ACE), caffeine (CAF), cefalexin (CLX) and sulfamethoxazole (SMX). It was found that GA plus EC/EF process yielded the following removal efficiencies: DnBP, 89 ± 2%; DEHP, 85 ± 3%; ACE, 99 ± 2%; CAF, 94 ± 3%; CLX, 100 ± 0%; and SMX, 98 ± 2%. Carbon adsorption, size exclusion, electrostatic repulsion, electrocoagulation, and electrofiltration were considered as the main mechanisms for the removal of target ECs by the integrated process indicated above.

Achieving zero waste of municipal incinerator fly ash by melting in electric arc furnaces while steelmaking.

The main objective of this work was to promote zero waste of municipal incinerator fly ash (MIFA) by full-scale melting in electric arc furnaces (EAFs) of steel mini mills around the world. MIFA, generally, is considered as a hazardous waste. Like in many countries, MIFA in Taiwan is first solidified/stabilized and then landfilled. Due to the scarcity of landfill space, the cost of landfilling increases markedly year by year in Taiwan. This paper presents satisfactory results of treating several hundred tons of MIFA in a full-scale steel mini mill using the approach of "melting MIFA while EAF steelmaking", which is somewhat similar to "molten salt oxidation" process. It was found that this practice yielded many advantages such as (1) about 18wt% of quicklime requirement in EAF steelmaking can be substituted by the lime materials contained in MIFA; (2) MIFA would totally end up as a material in fractions of recyclable EAF dust, oxidized slag and reduced slag; (3) no waste is needed for landfilling; and (4) a capital cost saving through the employment of existing EAFs in steel mini mills instead of building new melting plants for the treatment of MIFA. Thus, it is technically feasible to achieve zero waste of MIFA by the practice of this innovative melting technology.

Biocompatibility assessment of nanomaterials for environmental safety screening.

In view of the extensive use of nanoparticles in countless applications, a fast and effective method for assessing their potential adverse effects on the environment and human health is extremely important. At present, in vitro cell-based assays are the standard approach for screening chemicals for cytotoxicity because of their relative simplicity, sensitivity, and cost-effectiveness compared with animal studies. Regrettably, such cell-based viability assays encounter limitations when applied to determining the biological toxicity of nanomaterials, which often interact with assay components and produce unreliable outcomes. We have established a cell-impedance-based, label-free, real-time cell-monitoring platform suitable for use in a variety of mammalian cell lines that displays results as cell index values. In addition to this real-time screening platform, other traditional cytotoxicity assays were employed to validate cytotoxicity assessments. We suggest that the cell impedance measurement approach is effective and better suited to determining the cytotoxicity of nanomaterials for environmental safety screening. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 1170-1182, 2017.

Degradation of phthalate esters and acetaminophen in river sediments using the electrokinetic process integrated with a novel Fenton-like process catalyzed by nanoscale schwertmannite.

The main objective of this study was to develop and establish an in situ remediation technology coupling nano-schwertmannite/H2O2 process and electrokinetic (EK) process for the removal of phthalates (PAEs) and acetaminophen in river sediments. Test results are given as follows: (1) injection of nano-schwertmannite slurry and H2O2 (collectively, "novel oxidant") into the anode reservoir would yield ·OH radicals that then will be diffused into the sediment compartment and further transported by the electroosmotic flow and/or electrophoresis from the anode end toward the cathode to degrade PAEs and pharmaceuticals in the sediment if any; (2) an electric potential gradient of 1.5 V cm(-1) would help the removal of PAEs and acetaminophen in the blank test, which no "novel oxidants" was added to the remediation system; (3) the practice of electrode polarity reversal would maintain neutral pH for sediment after remediation; (4) injection of equally divided dose of 10 mL novel oxidant into the anode reservoir and four injection ports on the top of sediment chamber would further enhance the removal efficiency; and (5) an extension of treatment time from 14 d to 28 d is beneficial to the removal efficiency as expected. In comparison, the remediation performance obtained by the EK-assisted nano-SHM/H2O2 oxidation process is superior to that of the batch degradation test, but is comparable with other EK integrated technologies for the treatment of same contaminants. Thus, it is expected that the EK-assisted nano-SHM/H2O2 oxidation process is a viable technology for the removal of phthalate esters and pharmaceuticals from river sediments in large-scale operations.

Performance and mechanisms for the removal of phthalates and pharmaceuticals from aqueous solution by graphene-containing ceramic composite tubular membrane coupled with the simultaneous electrocoagulation and electrofiltration process.

In this study, commonly detected emerging contaminants (ECs) in water, including di-n-butyl phthalate (DnBP), di(2-ethylhexyl) phthalate (DEHP), cephalexin (CLX), sulfamethoxazole (SMX) and caffeine (CAF), were selected as the target contaminants. A lab-prepared graphene-containing ceramic composite tubular membrane (TGCCM) coupled with the simultaneous electrocoagulation and electrofiltration process (EC/EF) in crossflow filtration mode was used to remove target contaminants in model solution. Meanwhile, a comparison of the removal efficiency was made among various tubular composite membranes reported, including carbon fibers/carbon/alumina composite tubular membrane (TCCACM), titania/alumina composite tubular membrane (TTACM) and alumina tubular membrane (TAM). The results of this study showed that the removal efficiencies for DnBP and DEHP were 99%, whereas 32-97% for cephalexin (CLX), sulfamethoxazole (SMX) and caffeine (CAF). In this work the mechanisms involved in removing target ECs were proposed and their roles in removing various ECs were also discussed. Further, two actual municipal wastewaters were treated to evaluate the applicability of the aforementioned treatment technology (i.e., TGCCM coupled with EC/EF) to various aqueous solutions in the real world.

Removal of phthalates and pharmaceuticals from municipal wastewater by graphene adsorption process.

In this work graphene was used for evaluation of its adsorption behavior and performance in removing phthalate esters and pharmaceuticals in municipal wastewater. Di-n-butyl phthalate (DnBP), di-(2-ethylhexyl) phthalate (DEHP), acetaminophen (ACE), caffeine (CAF), cephalexin (CLX), and sulfamethoxazole (SMX) were emerging contaminants (ECs) with detection frequencies over 92% in a one-year monitoring of the occurrence of ECs in influent samples of a sewage treatment plant in Taiwan. Thus, these ECs were selected as the target contaminants for removal by graphene adsorption process. Experimental results showed that the adsorption isotherm data were fitted well to Langmuir model equation. It was also found that the adsorption process obeyed the pseudo-second-order kinetics. A graphene dosage of 0.1 g/L and adsorption time of 12 h were found to be the optimal operating conditions for the ECs of concern in model solutions in a preliminary study. By using the determined optimal operating conditions for removal of such ECs in actual municipal wastewater, removal efficiencies for various ECs were obtained and given as follows: (1) DnBP, 89%, (2) DEHP, 86%, (3) ACE, 43%, (4) CAF, 84%, (5) CLX, 81%, and (6) SMX, 34%.

Remediation of phthalates in river sediment by integrated enhanced bioremediation and electrokinetic process.

The objective of this study was to evaluate the feasibility of enhanced bioremediation coupling with electrokinetic process for promoting the growth of intrinsic microorganisms and removing phthalate esters (PAEs) from river sediment by adding an oxygen releasing compound (ORC). Test results are given as follows: Enhanced removal of PAEs was obtained by electrokinetics, through which the electroosmotic flow would render desorption of organic pollutants from sediment particles yielding an increased bioavailability. It was also found that the ORC injected into the sediment compartment not only would alleviate the pH value variation due to acid front and base front, but would be directly utilized as the carbon source and oxygen source for microbial growth resulting in an enhanced degradation of organic pollutants. However, injection of the ORC into the anode compartment could yield a lower degree of microbial growth due to the loss of ORC during the transport by EK. Through the analysis of molecular biotechnology it was found that both addition of an ORC and application of an external electric field can be beneficial to the growth of intrinsic microbial and abundance of microflora. In addition, the sequencing result showed that PAEs could be degraded by the following four strains: Flavobacterium sp., Bacillus sp., Pseudomonas sp., and Rhodococcus sp. The above findings confirm that coupling of enhanced bioremediation and electrokinetic process could be a viable remediation technology to treat PAEs-contaminated river sediment.

Occurrence of triclosan in the tropical rivers receiving the effluents from the hospital wastewater treatment plant.

The objective of this study was to determine the occurrence of triclosan in the tropical rivers where received the effluents from a hospital wastewater treatment plant (HWWTP) in southern Taiwan. Three and ten sampling sites were selected at the Jiaosu River (S0-S2) and Dian-Bao River (S3-S12), respectively. The samples of the HWWTP influent, effluent and receiving river water and sediment were collected and analyzed using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/ MS). Results showed that the triclosan level in surface water of the Jiaosu River and Dian-Bao River ranged from 3 to 68 ng/L and ranged from <2.7 to 51 ng/L, respectively. The hospital did contribute a loading of triclosan to the neighboring river. The mean value of triclosan concentration in the downstream surface water of the Jiaosu River (S1 20.2 ng/L) was approximately three times higher than that of the background level (S0 6.0 ng/L) (p = 0.011). The concentrations of triclosan in two surface water samples were over the predicted no effect concentration (PNEC) of 50 ng/L for algae. In addition, significant seasonal differences of triclosan in surface water of Jiaosu River (p = 0.020) and the HWWTP effluents (p = 0.302) were also observed. The concentrations of triclosan in sediments of these two rivers seemed stable. On average, triclosan was detected in 86 % of the sediment samples with a range from <1.1 to 13 ng/g. Triclosan in surface water and sediments of the tropical rivers might be rapidly photolyzed due to plenty of sunshine. It is worth to further investigate the occurrence and fate of triclosan photoproduct in the aquatic environment of the tropics.

Monitoring and removal of residual phthalate esters and pharmaceuticals in the drinking water of Kaohsiung City, Taiwan.

This study monitored the occurrence and removal efficiencies of 8 phthalate esters (PAEs) and 13 pharmaceuticals present in the drinking water of Kaohsiung City, Taiwan. The simultaneous electrocoagulation and electrofiltration (EC/EF) process was used to remove the contaminants. To this end, a monitoring program was conducted and a novel laboratory-prepared tubular carbon nanofiber/carbon/alumina composite membrane (TCCACM) was incorporated into the EC/EF treatment module (collectively designated as "TCCACM-EC/EF treatment module") to remove the abovementioned compounds from water samples. The monitoring results showed that the concentrations of PAEs were lower in water samples from drinking fountains as compared with tap water samples. No significant differences were found between the concentrations of pharmaceuticals in the two types of water samples. Under optimal operating conditions, the TCCACM-EC/EF treatment module yielded the lowest residual concentrations, ranging from not detected (ND) to 52ng/L for PAEs and pharmaceuticals of concern in the tap water samples. Moreover, the performance of the TCCACM-EC/EF treatment module is comparable with a series of treatment units employed for the drinking fountain water treatment system. The relevant removal mechanisms involved in the TCCACM-EC/EF treatment module were also discussed in this work.

Monitoring of PAEMs and beta-agonists in urine for a small group of experimental subjects and PAEs and beta-agonists in drinking water consumed by the same subjects.

This 5-month study contains two parts: (1) to monitor the concentrations of 11 phthalate esters metabolites (PAEMs) and two beta-agonists in human urine samples collected from a small group of consented participants including 16 females and five males; and (2) to analyze the residues of phthalate esters (PAEs) and beta-agonists in various categories of drinking water consumed by the same group of subjects. Each category of human urine and drinking water had 183 samples of its own. The analytical results showed that nine PAEMs were detected in human urine and eight PAEs were detected in drinking water samples. It was found that average concentrations of PAEMs increased as the age increased, but no significant difference between sexes. Further, using the principal component analysis, the loadings of age effect were found to be two times greater than that of gender effect in terms of four DEHP metabolites. Regarding beta-agonists of concern (i.e., ractopamine and salbutamol), they were neither detected in human urine nor drinking water samples in this study.

Electrokinetically enhanced removal and degradation of nitrate in the subsurface using nanosized Pd/Fe slurry.

The aim of this work was to evaluate the effectiveness of transporting the slurry of Pd/Fe bimetallic nanoparticles under an electric field in the subsurface for in situ removal and degradation of nitrate. To mimic the subsurface environment, a bench-scale horizontal column packed with nitrate-contaminated soil was treated by electrokinetic (EK) remediation coupled with the injection of nanosized Pd/Fe slurry. The estimated transport distance of Pd/Fe nanoparticles in soil based on the calculated sticking coefficient was about 9 meters by the enhancement of electrokinetics, primarily by electroosmotic (EO) flow. By injecting the nanosized Pd/Fe slurry into the anode reservoir coupled with the application of an electric field (i.e., Test 2) would result in the greatest overall removal efficiency of nitrate in soil and reservoir fluids as compared with other injection positions, the cathode reservoir being the worst injection spot. In Test 2, over 99% of nitrate in the whole system was removed and degraded even only 0.05 wt% of nanoscale Pd/Fe bimetal was injected.

Chemical reduction of nitrate by nanosized iron: kinetics and pathways.

This study was conducted to investigate chemical reduction of nitrate by nanoscale zero-valent iron (ZVI) in aqueous solution and related kinetics and pathways. In the last decade, employment of micro-scale ZVI has gained its popularity in nitrate reduction. To further study chemical reduction of nitrate, nanosized iron was synthesized and tested in this work. It has a size in the range of 50-80 nm and a BET surface area of 37.83 m(2)g(-1). Chemical reduction of nitrate by nanosized iron under various pHs was carried out in batch experiments. Experimental results suggest that nitrate reduction by nanosized ZVI primarily is an acid-driven surface-mediated process. A stronger acidic condition is more favorable for nitrate reduction. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. Additional test results also showed that the reduction rate of nitrate increased as the dose of nanosized ZVI increased. In all tests, reaction rate equations developed do not obey the first- or pseudo-first-order reaction kinetics with respect to the nitrate concentration. Based on the research findings obtained, two possible reaction pathways for nitrate reduction by nanoscale iron particles have been proposed in this work.

Crossflow electro-microfiltration of oxide-CMP wastewater.

In this work, an electrically enhanced crossflow microfiltration (EECMF) system was used for the treatment of oxide-CMP wastewater under different operating conditions to investigate their effects on filtration rate. Oxide-CMP wastewater was obtained from a wafer fab and characterized by various standard methods. A membrane with a cut size of 0.1microm was used in the EECMF system. Operating parameters studied include crossflow velocity, transmembrane pressure, mode of electric field, electric field strength, and mode of backwashing. The filtration rate was found to increase with increasing crossflow velocity, electric field strength, and transmembrane pressure when operated below the critical electric field strength. Experimental results indicated that intra-filtration-run backwashing outperformed inter-filtration-run backwashing in terms of filtration rate. Experimental results also showed that the filtration rate for pulsed mode operation was greater than that of no electric field application, but worse than that of continuous mode operation. Using the present EECMF system, a fairly good quality of filtrate was obtained. It was found that the filtrate having a turbidity of 0.39 NTU is achievable. Thus, the filtrate could be reused for non-process applications.